Synthetic detergent bar



United States Patent 3,231,606 SYNTHETKC DETERGENT EAR William A.Fessler, Rte. 1, Hopewell, Va. No Drawing. Filed Aug. 22, 1962, See. No.218,542 2 Claims. (Ci. fill-513) My invention relates to the productionof novel synthetic detergents by the sulfitation of ethylenehomopolymers, the detergents thus obtained having particular utility inthe making of synthetic detergent bars.

While synthetic detergents have found widespread use in powdered andliquid form, they have had little commercial success in displacing, inbar form, the familiar bars of household toilet soaps. This inability ofpresently available synthetic detergent bars to make any substantialinroads into the soap bar market is attributable to a number of factors.From an economic standpoint, synthetic deter-gents which aresufiiciently inexpensive to be considered for making bars and which havethe requisite lathering and cleansing power are, generally speaking,more soluble than the soaps utilized in the making of conventional soapbars. Furthermore, most synthetic detergents do not become plastic, andthe machinery for fabricating satisfactory bars from such substancesmust be specially designed. Still further, conventional syntheticdetergent bars tend to develop a slimy surface upon standing n contactwith a wet surface, and they do not possess the feel of ordinary toiletsoaps. Numerous efforts have been made to meet these and other problemsincluding the incorporation of considerable quantities of fillers suchas bentonite, starch, and the use of waxes for various purposesincluding that of attempting to impart a soap-like feel to the bars.

Another problem with certain synthetic detergents, particularly thealkylaryl sulfonates which now constitute the principal component ofmany of the widely used detergents, and which is becoming increasinglyserious, centers around problems of sewage disposal. Very smallquantitles of such detergents cause the formation of highly stable foamsin the aerators of sewage systems and greatly decrease the rate ofsettling of solid suspended matter. Such conditions hamper and add tothe costs of the sewage treating processes. These effects are believedto be due to the resistance of such detergents to breakdown byconventional biochemical sewage-treating processes. For these and otherreasons, it is important that detergents be biologically degradable byconventionally used sewage disposal techniques so that they may beremoved from Water undergoing sewage treatment.

In accordance with the present invention, 1 have discovered thatsynthetic detergents capable of being formed into a bar, particularlywithout the incorporation of inactive fillers or additives orappreciable proportions thereof, and which are biologically degradable,can be produced by the sulfitation of ethylene homopolymers,particularly those having from 12 to 14 carbon atoms. Such deter-gentsare sufiiciently plastic in character to permit them to be formed intobars with conventional machinery, and the bars themselves havesubstantially all of the characteristics of fatty acid derived soap barsnot only from the standpoint of surface feel but also with respect totheir lather producing and cleansing properties.

The ethylene homopolymers having utility for the purposes of myinvention are those which contain predominately l-alkenes having from 8to 22 carbon atoms, with especially desirable sulfitation detergentproducts being obtainable from such ethylene homopolymers, and mixturesthereof, having from 10 to 16, and, better still, from 12 to 14, carbonatoms in the molecule. They are essentially linear in structure but maycontain a few percent, say 2 to of branched chain materials. Suchbranched chain materials serve to increase resistance to water hardnessof the finished detergent products of this invention. The production ofthe ethylene homopolymer starting materials may be accomplished by anymethod known in the art. One such method, by way of illustration, is theZiegler procedure wherein ethylene is pass d into contact withtriethylaluminum at elevated temperatures. Particularly effectiveresults have been achieved in accordance with the practice of myinvention with commercial sources of such polymerized ethylenecomprising about or more, for instance, 92 to 97%, of said ethylenehomopolymers consisting essentially of 1- alkenes, said commercialsources containing minor amounts of other materials which apparentlyhave no observable adverse effects on the properties of the ultimatesynthetic detergent products. The term ethylene homopolymers,- as usedherein and in the claims, will, accordingly, be understood to mean suchethylene homopolymers as contain predominately l-alkenes and which aremainly of linear character.

In my prior US Patent 2,653,970, there is described a process forproducing detergents by the addition of water-soluble bisulfites toolefins containing from about 10 to 22 carbon atoms. The olefinsdisclosed and utilized in the practice of the process of that patentwere derived from cuts obtained by cracking aliphatic higher waxypetroleum fractions such as petrolatum, and also from cuts of olefinsobtained by the Fischer-Tropsch synthesis. While the detergents producedin accordance with the teachings of my prior patent were obtained inreasonably good yields, prolonged reaction times, for example, of theorder of 16 to 40 hours, or more, were required. Moreover, thedetergents produced in accordance with said patent, while possessinggood detergent properties, as well as good color, low hygroscopicity,and good alkaline and acid stability, were not adequately satisfactoryfor fabrication into synthetic detergent bars, particularly essentiallyall-synthetic detergent bars.

I have made the surprising discovery that, if ethylene homopolymers ofthe type described above are reacted with Water-soluble bisulfites,synthetic detergents are produced having markedly improved propertiesfor the production of synthetic detergent bars, especially from thestandpoint of their ability to be formed into bars of substantially 100%active synthetic detergent having the appearance and surface feel of aconventional soap bar. I have also discovered, that, by employing theaforesaid ethylene homopolymers in the reaction with the watersolublebisulfites, the reaction proceeds at rates at least twice as fast aswith such olefins as are disclosed in my said prior patent, and, in manyinstances, up to 5 or more times faster than was possible utilizing sucholefins as are disclosed in my prior patent. Moreover, essentiallyquantitative yields of detergent are obtained based on inputhomopolymer, a matter of major economic importance, not only because itminimizes cost of raw material but also because it avoids the problem ofnon-detergent impurity which besets the customary routes to sulfonatedetergents. Hydrocarbon impurities contaminate the sulfonates frombisulfite addition to olefins made from carbon monoxide and hydrogen orby cracking higher hydrocarbons. Hydrocarbons and sulfones contaminatesulfonates made by reacting alkylaromatics with sulfur trioxide or othersulfonating agent. Unless removed, these impurities impair detergency,odor and other properties, yet their removal requires the signh'icantadded expense of such separate steps as adsorption, solvent extractionor prolonged steam distillation. Accordingly, a synthesis which avoidsthese impurities, as does the present one, represents a marked advance.

The procedural steps per se, for the production of the novel and usefulsynthetic detergents of my present invention, may, generally speaking,follow those disclosed in my aforesaid prior patent. Thus, the reactionmixture may comprise water; the ethylene homopolymer (or mixturesthereof) having from 8 to 22 carbon atoms; a watersoluble bisulfite; analkaline agent, especially an alkali metal sulfite, to maintain theaqueous phase of the mixture at the desired pH level; a polar organicsolvent; and, advantageously, a water-soluble synthetic detergent ororganic surface active agent. The reaction is induced by dispersing agas containing molecular oxygen, particularly desirably air, through thereaction mixture.

The water-soluble bisulfite employed as the sulfitating agent in thepractice of my present invention may be an alkali metal bisulfite suchas and especially sodium bisulfite, but other water-soluble bisulfitesexemplified by ammonium bisulfite or aliphatic amine or pyridinebisulfites may be used. Furthermore, compounds which, in solution, areconverted to bisulfites can be used as, for example, sodiummetabisulfite (Na S O which, in the presence of water, is converted tosodium bisulfite (NaHSO While control of pH may be effected by variousalkalies or alkaline reagents, it is especially desirable to use alkalimetal sulfites, such as sodium sulfite. The pH of the aqueous phase ofthe starting reaction mixture is advantageously between about 6 or 6.5and about 7.5, as measured with a glass electrode at 30 C. During thereaction proper, the pH is maintained above 6 and below 9 as measuredwith a glass electrode at 30 C.

The polar organic solvent is advantageously a watersoluble volatilealcohol containing at least 3 carbon atoms or any other water-solublevolatile liquid can be used such as ethanol; propanol; isopropanol;butanol; isobutanol; pentanols; hexanol; dioxane; methyl, ethyl, andbutyl mono-others of ethylene glycol; and aliphatic amines such asethylamine, propyl amine and isopropyl amine. The polar organic solventused should be essentially nonreactive under the process conditionsemployed. Convenience of recovery of the polar organic solvent is animportant practical consideration. If air is used, as distinguished frompure oxygen in the'reaction, excessive solvent loss will occur duringthe reaction period if the solvent has a normal boiling point belowabout 60 C. While this loss can be avoided by putting the reactionsystem under pressure or by passing the efiluent air through anadsorbent system, it is preferred to avoid such procedures. Generallyspeaking, the solvent desirably should not have a boiling point in arange that requires the use of excessive quantities of heat and/ornegative pressure to accomplish removal thereof of distillation. Hence,from the standpoint of these practical considerations, the normalboiling point of the solvent should not exceed about 150 C. and isadvantageously in the range of 70 to 100 C.

The quantity of polar organic solvent employed in the process of mypresent invention may vary within wide limits. Generally speaking,excesses should be avoided to reduce distillation times to a minimum.Desirably the quantities of solvent utilized in my present process willrange from 1 to 8 mols, usually from 4 to 6 mols, per 100 mols of waterused in forming the reaction mixture.

The use of a water-soluble surface active agent or synthetic detergentin the practice of my present invention, while not essential, is highlydesirable as will be made clear hereinafter. The surface active agentused may be obtained from previous runs, or may be any of a number ofcommercially available products. I have found that effective results canbe attained by adding a small quantity of a liquid detergent product,for in-.

stance, an alkylaryl sulfonate, such as that sold under the trade nameVel (Colgate-Palmolive Company). Alkyl aryl sulfonates, such as dodecylbenzene sodium sulfonate, tridecyl benzene sodium sulfonate, andpentadecyl benzene sodium sulfonate; alcohol sulfates such as parativelyhigh C are used, may also be present.

, inorganic anions in the lower.

lauryl sodium sulfate and myristyl sodium sulfate; lauric acid amide oftaurine (sodium salt); and lauric acid ester of sodium isethionate areillustrative of numerous other surface active agents which can be usedwith good results. The amount of the water-soluble surface active agentemployed is generally in the range of from 40 to 200 grams, usuallyabout grams of the surface active agent, based on its content of activematerial, per mol of the ethylene homopolymer in the reaction mixture.

Generally speaking, the reaction mixtures of my present invention, atthe start of the reaction, may be present in (a) systems of three liquidphases wherein, so far as ascertained, the top phase comprises anethylene homopolymer-rich phase, the'intermediate phase is onecontaining all of the components of the reaction mixture with the polarorganic solvent predominating, and the lower phase is rich in water andinorganic salts; or (b) systems of two liquid phases. Good yields of thenovel detergents of my present invention are obtained in systems ofthree liquid phases regardless of whether a surface-active agent isinitially present, but with systems of two liquid phases good yieldshave been obtained only when such an agent has been added at the startof the reaction period. A system of three liquid phases is obtained bymixing the ethylene homopolyrner and a concentrated aqueous solution ofthe water-soluble bisulfite and sulfite and gradually adding, withstirring, the volatile polar organic solvent, periodically allowingsettling to verify that three liquid phases are present. Three-phasesystems may also be present Where surface active agents or syntheticdetergents are utilized in the reaction mixtures. As reaction proceeds,in batch operation, the top layer in a system of three liquid phasesdisappears.

Upon completion of reaction, sulfitations of ethylene homopolymerscontain either one or two liquid phases. Solid, which may be eithersodium sulfite or sodium sulfate if sodium salts and small amounts ofwater .are used, or alkane sulfonates if ethylene homopolymers of com-The high C sulfo-nates may be brought into solution by Warming.

If a product containing the salts of inorganic anions is wanted, thereaction mixture is adjusted to a pH of about 8, heated to distill offthe volatile, polar organic solvent for reuse, and the remainingdetergent solution is then either used as is or dried to a white solid.

For some purposes, as in production of bars for household use, a productfree of salts of inorganic anions is preferable. This may be prepared byadiusting the content of volatile organic solvent in the final reactionmixture until two liquid phases are obtained with most of the detergentin the upper layer and most of the salts of To achieve the desireddisposition between the two layers, in some cases more solvent should beadded at the end of a sulfitation; in others some of the solvent alreadypresent should be distilled off. Simple testing on small portions of thefinal reaction mixture is usually indicated to determine which should bedone. After separation of the liquid layers, the volatile organicsolvent is distilled from each and recovered for reuse. The upper layermay then be dried, either completely or with only partial removal ofwater, to provide solid organic sulfonate essentially free of salts ofinorganic anions. This material may be converted into bars by methodsconventional in the soap industry. The lower layer may be dried toafford valuable byproduct salts.

It is highly desirable, at least in certain cases, in the recovery ofthe novel synthetic detergents of my present invention, after thesulfitation reaction has been completed, to remove the upper ethylenehomopolymer-bisulfite reaction product-rich phase by, for example,decantation, and subject this phase to a conventional distillationoperation to remove solvent. The solvent, as is the case in all of thedistillation operations utilized in my present invention, is circulatedthrough the system for reuse. Some sodium sulfate is obtained in thereactions and can be utilized as a valuable by-product.

Whether the initial reaction medium exists a a threephase or two-phasesystem is not critical to the properties of the novel syntheticdetergents obtained in accordance with the practice of this invention.The polar organic solvent, and the initially present surface activeagent or synthetic detergent where used, are utilized in the formationwithin the reaction mixture of a liquid phase in which two reactants,that is, the ethylene homopolymer and the Water-soluble bisulfite, aresigni icantly soluble. The provision of such a liquid phase for thereactants is directly connected to the extent of completion of theaddition reaction between the Water-soluble bisulfite and the ethylenehomopolymer. Unless such a liquid phase is present, the oxygen requiredto induce the addition will oxidize the bisulfite and the sulfite ionspresent to the corresponding sulfate (and to a small amount ofdithionate), with the result that practically none, or at least verylittle, of the desired synthetic detergent will be formed.

The molecular oxygen-containing gas employed as an inducing agent in mypresent process may be introduced into the reaction mixture in anymanner known in the art, and may, as disclosed in my prior patent, beair or relatively pure oxygen.

The temperatures at which the addition reaction takes place may rangebetween about room temperature and the reflux temperature of thereaction mixture. Very satisfactory results have been attained attemperatures ranging from C. to 60 C. Usually, however, temperatures inthe range of C. to C. are adequate. Lower temperatures raise coolingcosts; and higher temperatures produce increased costs since moreorganic solvent must be condensed and returned to the reaction mixture.

The reactionv may be carried out at either atmospheric orsuperatm-ospheric pressure. The quantity of solvent removed from thereaction mixture by a given weight of exit gas is approximatelyinversely proportional to the absolute pressure on the system and thiswill in some cases warrant the expense of operation at a pressure atleast modestly above atmospheric.

The relative proportions of water, water-soluble bisulfite andwater-soluble sulfite or other alkaline material employed in my presentprocess correspond substantially to those of my prior patented process.Thus, the bisulfite is employed in amounts of from about 1 to 2.5 mols,especially desirably from about 1 to 2 mols, per mol of ethylenehomopolymer used. Amounts of the order of 3 mols may be used, but suchis not particularly practical.

The Water-soluble sulfite is desirably employed in a mol ratio to thewater-soluble bisulfite in the range of about 1:1 to 3:1. Such molratios determine the particular pH of the mixture at the start of thereaction. Where alkaline materials other than water-soluble whites areemployed, the amounts thereof should be selected so as to produce thedesired pH.

The quantity of water used in the reaction mixture advantageously rangesfrom about 25 to 75 mols per mol of ethylene homopolymer.

In order that those skilled in the art may even more fully understandthe nature and advantages of my present invention, I shall describe afew illustrative examples for carrying out my invention. It will beunderstood, however, that the same are not to be construed in any way aslimitative of the true scope of my invention, the latter being pointedout in the claims. It will be understood that variations may be made,among other things, in the nature of the ethylene homopolymers, thepolar organic solvents used, and the surface active agents, if any,employed. Those skilled in the art will, in the light of my teachingsherein, be able to make various adjustments all of which will fallwithin the scope of my novel teachings.

, mixture.

5 Example 1 A mixture was formed of 0.2 gram mol of an ethylenehomopolyrner containing predominately 16 carbon atoms, 0.15 gram mol ofsodium metabisulfite (Na S O 0.5 gram mol of sodium sulfite, grams oftertiary butyl alcohol, 270 grams of water and 10 grams of a detergentsold under the trademark Vel. Initially three phases were discernible inthe mixture together with a small amount of undissolved inorganic salt.The sulfitation reaction was allowed to proceed at room temperature(about 22 C.) for 5 hours. Agitation throughout the reaction period wasprovided by a kitchen-type electrical mixer. Molecular oxygen to inducethe addition of the bisulfite to the ethylene homopolymer came from airbeaten into the mixture by the mixer.

Samples were periodically removed from the reaction mixture, warmed, anddiluted with water. Unreacted ethylene homopolymer showed up asturbidity. When turbidity was no longer evident, the reaction wasallowed to proceed an additional hour to make certain that the ethylenehomopolymer had completely reacted. The ethylene homopo-lymer-bisulfitereaction product appeared in the form of a white, waxy solid suspendedthrough the reaction mixture. The pH of the reaction mixture wasadjusted to 8 with sodium bicarbonate and the mixture was evaporated todryness. The final product was a white, friable solid which produced atfoaming solution when a small portion was added to hot water.

Example 2 A mixture was formed as described in Example 1, but, in placeof the ethylene homopolymer thereof, an ethylene homopolymer containingpredominately 14 carbon atoms was used, and, instead of Vel, a likequantity of the synthetic detergent obtained in Example 1 was used.Initially three phases were present in the mixture along with a smallamount of undissolved inorganic salt. The reaction was allowed toproceed for 4 hours at room temperature. Agitation with the concomitantaddition of molecular oxygen was provided as in Example 1. The reactionmixture was a thick, creamy paste. The pH was adjusted to 8 by sodiumbicarbonate and water and alcohol removed by evaporation. The finalproduct had properties similar to those of the product obtained inExample 1 but was slightly more soluble in water and foamed morecopiously.

Example 3 A mixture was formed as described in Example 1, but using asthe ethylene homopolymer one containing predominately 12 carbon atoms,and the detergent obtained from the run of Example 2 was used as thesurface active seeding agent. Initially two phases were present in theThe reaction was allowed to proceed at room temperature for a total of 8hours. The pH was adjusted to 8 by sodium bicarbonate and the water andthe alcohol evaporated. A white, friable solid was obtained whichdissolved in cool water to give foaming solutions that were opalescent.The solutions became clear upon warming.

Example 4 A run similar to that of Example 3 was made but using as theethylene homopolymer one containing predominately 10 carbon atoms, andthe synthetic detergent obtained from Example 3 was used as the surfaceactive agent. Two phases were present initially. The reaction time was 4hours. A white, friable solid product resulted, being soluble in coolwater to form foaming solutions.

Example 5 A. run similar to that of Example 3 was made but using as theethylene homopolymer one containing predominately 8 carbon atoms, andthe synthetic detergent obtained from Example 4 was used as the surfaceactive agent. Two liquid phases were present initially. The reactiontime was 8 hours. During the reaction period the upper liquid layergradually increased from one third to one half the total volume. Thefinal product was a white, friable solid readily soluble in. cool water.Such a solution foamed readily when shaken but the foam broke rapidly.

Example 6 One part of each of the products obtained in Examples 2 and 3above was mixed together and added to 3 parts of water and 2 parts oftertiary butyl alcohol, said parts being by weight. The mixture wasstirred at room temperature and produced two liquid phases withconsiderable solid suspended in the lower one thereof. The upper liquidphase was drawn off and the solvent evaporated. From this there wasobtained slightly less than 1 part of a white, soap-like solid that,when slightly moist, could be molded with the hands into a bar. Whendry, the bar had a number of very desirable characteristics. It readilyremoved dirt from the hands, it gave a stable lather, it felt like aconventional soap bar, and it retained its firmness during the processof wetting and handling to which a conventional soap bar is normallysubjected. After use, the bar imbibed the residual water, soonpresenting a firm surface.

Example 7 A mixture was formed of 0.1 gram mol of an ethylenehomopolymer containing predominately 14 carbon atoms, 0.1 gram mol of anethylene homopolymer containing predominately 12 carbon atoms, 28.5grams of sodium metabisulfite (Na S O 63 grams of sodium sulfite, 270grams of water, and 65 grams of tertiary butyl alcohol. After mixing atroom temperature, two liquid phases were present, 25 grams of asynthetic detergent bar made in accordance with Example 6 were added anddissolved by stirring. Two liquid phases were still present, the upperoccupying about 40% of the total volume. During a five hour reaction(stirring at room temperature, exposed to air), the volume of the upperphase gradually increased until it was about 75% of the total, holdingat this value during the latter part of the run. The lower, salt-rich,phase was discarded. (In commercial operations, this lower phase may betreated to recover the alcohol, the sodium sulfite and sodium sulfate.)The upper phase was evaporated to a thick, White paste which was formedinto a bar and cooled. The crude, moist bar, weighing about 200 grams,was redissolved at room temperature in 200 grams tertiary butyl alcoholand 50 grams H O. Again two liquid phases were formed along with alittle solid that settled to the bottom and appeared to be crystalline,inorganic salt, presumably either sodium sulfate or sodium sulfite. Theclear upper layer was drawn oil? and the solvent evaporated therefrom.While still somewhat moist and warm it was shaped into a bar with aspatula. It was white, firm when cooled and formed a lather when usedfor washing the hands.

Bar products formed from the synthetic detergents obtained in accordancewith my present invention have the smooth surface feel which is referredto in the art as good slip or finish? They manifest quite highresistance to water hardness. Because of their essentially neuturalcharacter they do not affect the slight acidity of the skin as doconventional soaps.

It will be understood that various changes and modifications may be madewithout departing from the spirit of this invention.

What I claim as new and desire to protect by Letters Patent of theUnited States is:

1. A synthetic detergent bar containing as the essential syntheticdetergent agent thereof a solid reaction product of a Water-solublebisulfite with an ethylene homopolymer containing predominatelyl-alkenes which are mainly linear in character and have a few percent ofbranched chain materials and containing from 10 to 16 carbon atoms, saidsynthetic detergent agent being prepared by a process comprising forminga reaction mixture comprising an ethylene homopolymer containingpredominately l-alkenes which are mainly linear in character and have afew percent of branched chain materials and containing. from 10 to 16carbon atoms, water, a water-soluble volatile polar organic solvent, awater-soluble bisulfite, and an alkaline material, the aqueous phase ofsaid reaction mixture having a pH between about 6 and about 7.5, the molratio of said bisulfite to said ethylene homopolymer being in the rangeof 1:1 to 3:1, and dispersing a gas containing molecular oxygen throughsaid reaction mixture, the reaction mixture being maintained at atemperature between about room temperature and the reflux temperature'ofthe reaction mixture, the pH in the aqueous phase being maintained aboveabout 6 and below about 9.

2. An all synthetic detergent bar containing as the essential syntheticdetergent agent thereof a reaction product of sodium bisulfite with anethylene homopolymer containing predominately l-alkenes which are mainlylinear in character and have a few percent of branched chain materialsand containing from 12 to 14 carbon atoms, said synthetic detergentagent being prepared by a process comprising forming a reaction mixturecomprising an ethylene homopolymer containing predominately 1- alkeneswhich are mainly linear in character and have a few percent of branchedchain materials and containing from 12 to 14 carbon atoms, water, awater-soluble volatile polar organic solvent, a water-soluble bisulfite,and an alkaline material, the aqueous phase of said reaction mixturehaving a pH between about 6 and about 7.5, the mol ratio of saidbisulfite to said ethylene homoploymer being in the range of 1:1 to 3:1,and dispersing a gas containing molecular oxygen through said reactionmixture, the reaction mixture being maintained at a temperature betweenabout room temperature and the reflux temperature of the reactionmixture, the pH in the aqueous phase being maintained above about 6andbelow about 9.

References Cited by the Examiner UNITED STATES PATENTS 2,318,036 5/ 1943Werntz 260513 2,504,411 4/1950 Harman 2605 13 2,653,970 9/ 1953 Fessler2605 13 3,084,186. 5/ 1963 Clippinger 2605 13 LORRAINE A. WEINBERGER,Primary Examiner, LEON ZITVER, Examiner.

B. M. EISEN, Assistant Examiner.

1. A SYNTHETIC DETERGENT BAR CONTAINING AS THE ESSENTIAL SYNTHETICDETERGENT AGENT THEREOF A SOLID REACTION PRODUCT OF A WATER-SOLUBLEBISULFITE WITH AN ETHYLENE HOMOPOLYMER CONTAINING PREDOMINATELY1-ALKENES WHICH ARE MAINLY LINEAR IN CHARACTER AND HAVE A FEW PERCENT OFBRANCHED CHAIN MATERIALS AND CONTAINING FROM 10 TO 16 CARBON ATOMS, SAIDSYNTHETIC DETERGENT AGENT BEING PREPARED BY A PROCESS COMPRISING FORMINGA REACTION MIXTURE COMPRISING AN ETHYLENE HOMOPOLYMER CONTAININGPREDOMINATELY 1-ALKENES WHICH ARE MAINLY LINEAR IN CHARACTER AND HAVE AFEW PRECENT OF BRANCHED CHAIN MATERIALS AND CONTAINING FROM 10 TO 16CARBON ATOMS, WATER, A WATER-SOLUBLE VOLATILE POLAR ORGANIC SOLVENT, AWATER-SOLUBLE BISULFITE, AND AN ALKALINE MATERIAL, THE AQUEOUS PHASE OFSAID REACTION MIXTURE HAVING A PH BETWEEN ABOUT 6 AND ABOUT 7.5, THE MOLRATIO OF SAID BISULFITE TO SAID ETHYLENE HOMOPOLYMER BEING IN THE RANGEOF 1:1 TO 3:1, AND DISPERSING A GAS CONTAINING MOLECULAR OXYGEN THROUGHSAID REACTION MIXTURE, THE REACTION MIXTURE BEING MAINTAINED AT ATEMPERATURE BETWEEN ABOUT ROOM TEMPERATURE AND THE REFLUX TEMPERATURE OFTHE REACTION MIXTURE, THE PH IN THE AQUEOUS PHASE BEING MAINTAINED ABOVEABOUT 6 AND BELOW ABOUT 9.